Polyhaloalkylpolythioalkyl sulfite esters

ABSTRACT

ESTERS AND ETHERS OF THE FORMULA   ROXSMR&#39;&#39;   WHERE R&#39;&#39; REPRESENTS A POLYHALOALKYL GROUP HAVING 1 TO 2 CARBON ATOMS AND 3 TO 5 HALOGENS OF ATOMIC NUMBER 17 TO 35, AT LEAST ONE OF SAID HALOGENS BEING BONDED TO THE ALPHA CARBON ATOMS, X IS ALKYLENE OF 1 TO &#39;&#39; CARBON ATOMS AND M IS AN INTEGER VARYING FROM 2 TO 3, AND R IS AN ORGANIC RADICAL WHICH FORMS AN ESTER OF ETHER WITH THE REMAINDER OF THE MOLECULE. TYPICAL R GROUPS ARE HYDROCARBYL, PHOSPHORO, CARBONYL, OXYCARBONYL, SULFATE AND SULFONATE GROUPS. THE ESTERS AND ETHERS ARE USEFUL AS FUNGICIDES.

3,632,622 POLYHALOALKYLPOLYTHIOALKYL SULFITE ESTERS Joseph E. Moore,Richmond, Calif., assignor to Chevron Research Company, San Francisco,Calif.

No Drawing. Application Oct. 20, 1966, Ser. No. 588,009,

now Patent No. 3,519,672, which is a continuation-inpart of applicationSer. No. 414,876, Nov. 30, 1964. Divided and this application Apr. 1,1969, Ser. No.

Int. Cl. C07c 137/00 US. Cl. 260-456 R Claims ABSTRACT OF THE DISCLOSUREEsters and ethers of the formula ROXS R where R represents apolyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens ofatomic number 17 to 35, at least one of said halogens being bonded tothe alpha carbon atoms, X is alkylene of 1 to 4 carbon atoms and m is aninteger varying from 2 to 3, and R is an organic radical which forms anester or ether with the remainder of the molecule. Typical R groups arehydrocarbyl, phosphoro, carbonyl, oxycarbonyl, sulfate and sulfonategroups. These esters and ethers are useful as fungicides.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a divisionalof copending application Ser. No. 588,009 filed Oct. 20, 1966, now US.Pat. No. 3,519,672, which is a continuation-in-part of US. applicationSer. No. 414,876, filed Nov. 30, 1964, and now abandoned.

This invention relates to novel esters and ethers which contain apolyhalo (lower) alkylpolythioalkyl group and their use as fungicides.

The compounds of this invention may be represented by the generalformula:

ROXS R' where R' represents a polyhaloalkyl group having 1 to 2 carbonatoms and 3 to 5 halogens of atomic number 17 to 35, at least one ofsaid halogens being bonded to the alpha carbon atom, X is alkylene of 1to 4 carbon atoms, m is an integer varying from 2 to 3, and R is anorganic radical which combined with OXS R forms an ether or ester.Halogens of atomic number 17 to 35 are chlorine and bromine. The alphacarbon atom of the polyhaloalkyl group is bonded to a sulfur of thepolysulfide (S group.

X is an alkylene group of from 1 to 4 carbons, e.g., methylene,ethylene, trimethylene, tetramethylene, isopropylene, 1,3-butylene, etc.The RO group is bonded to a primary carbon, that is, the carbon bondedto oxygen has two hydrogens. Preferred alkylene groups contain 2 to 3carbons.

The esters and ethers of this invention may be considered to bederivatives of alcohols. Thus, in a broad sense R is an organic radicalwhich forms a bond with oxygen and may be cleaved on hydrolysis toregenerate the alcohol as follows:

The R groups do not contribute significantly to the biological activityof the compounds of this invention. However, they may provide a meansfor special application or more attractive physical properties, e.g.hydrophobic, liphophilic, etc.

The R groups which form esters or ethers with OXS R' United StatesPatent 0 3,632,622 Patented Jan. 4, 1972 where R is a halohydrocarbylgroup having 0 to 1 halogens of atomic number 17 to 35 and 1 to about 8carbon atoms or a halohydrocarbylamino group having 0 to l halogens ofatomic number 17 to 35 and 1 to about 8 carbon atoms,

CYR

where Y is a chalcogen atom of atomic number 8 to 16, i.e. O and S, andR is a halohydrocarbyl group having 0 to 1 halogens of atomic number 17to 35 and 1 to about 8 carbon atoms or halophenylthioalkyl in which thehalogen is of atomic number 17 to 35,

where R is a hydrocarbyl group of 1 to about 6 carbon atoms,

where R is OXS R as defined above,

wgfl o Where R is OXS R' as defined above or alkyl, or

(f) alkyl or 1 to about 6 carbon atoms.

Examples of radicals which R may represent are alkyl such as methyl,ethyl, hexyl and octyl, butenyl, phenyl, benzyl, tolyl; haloalkyl suchas chloromethyl, chloroethyl, bromopropyl and chloroamyl,chloropropenyl, bromophenyl, chlorobenzyl, 4 chloro 6 methylphenyl;alkylamino such as methylamino, ethylamino, butylamino, hexylamino andchlorobutylamino, chlorophenylamino, bromophenylamino,6-bromo-2-methyl-phenylamino and the like.

Examples of specific groups which R may be are methyl, ethyl, isopropyl,hexyl, octyl, chloroethyl, chloropropyl, bromoamyl, chlorophenyl,bromobenzyl, chlorobutenyl, 6-chloro-2-methylphenyl,chlorophenylthioethyl, bromophenylthiopropyl, chlorophenylthiobutyl andthe like.

Examplees of R are methyl, ethyl, propyl, hexyl, propargyl, butenyl andphenyl.

Illustrative of the novel compounds of this invention are the followingcompounds:

,6-(trichloromethyldithio) ethyl benzoate;

B-(perchloroethyldithio)ethyl acetate;

,B-( 1, 1,2-trichloroethyldithio) ethyl benzoate;

fl- 1, 1,2,2-tetrachloroethyldithio) ethyl N-ethylcarbamate;

fl-( 1 ,2,2,Z-tetrachloroethyldithio ethyl butyrate;

di-v-( 1,1,2-trichloroethyldithio)-propyl carbonate;

'y-(1,1,2,2-tetrachloroethyldithio)-propyl S-ethyl thiolcarbonate;

v-(perchloroethyltrithio)-propyl hexanoate;

di- [B-( 1,2,2-trichloroethyldithio ethyl] sulfate;

di- ,8-( 1,2,2,2-tetrachloroethyldithio ethyl] sulfate;

ethyl [i-(1,1,Z-trichloroethyldithio)ethyl sulfate;

butyl 'y-(1-chloro-2,2-dibromoethyl)dithio propyl sulfate;

di B- (trichloromethyldithio ethyl] sulfite;

di['y-(1,1,2,2-tetrachloroethyldithio)propyl] sulfite;

0,0-dimethyl O-[fi-(perchloroethyldithio)ethyl] phosphate;

0,0-dipropyl O- [,8- 1,2,2-trichloroethyldithio ethyl] phosphate;

0,0-di-phenyl O- fi-( 1,1,2,2-tetrachloroethyldithio) ethyl] phosphate;

0,0-dimethyl O-[[3-(perchloroethyldithio)propyl] phosphate;

methyl-B-(trichlorornethyldithio)ethyl ether;

ethy1-'y-(1,1,2,2-tetrachloroethy1trithio)propyl ether;

amyl- -(perchloroethyldithio)propyl ether; and

hexyl-fi-(tribromomethyldithio)propyl ether.

Applications novel compounds may be prepared according to generalmethods known in the art. The esters may be prepared by condensing anappropriate w-polyhaloalkylpolythio alkanol with an appropriate acid.Acidic compounds such as acids, acid anhydrides, and acid halides may beused according to procedures known in the art. When desirable,transesterification may also be used. Etherification may be achievedwith sulfate esters, active halogen compounds and the alkoxide of thew-polyhaloalkylpolythio alcohol by methods known in the art. For makingsome of the compounds it may be preferable to prepare the oxygenderivative first and then contact the resulting mercaptan with thedesired polyhaloalkylthio or thiosulfenyl halide.

The alcohol precursors of the compounds of this invention may beprepared by reacting a mercapto alcohol with a polyhaloalkylsulfenyl or-thiosulfenyl halide. Temperatures in the range of to 50 C. may be used,but ambient temperatures or somewhat lower are preferred, that is,temperatures in the range of 0 to 25 C. Various solvents may be used inthe reaction which are inert to 4 the reactants and products. Preferredsolvents are halogenated hydrocarbons.

The following examples are offered as illustrative of the methods ofpreparation of the novel compounds of this invention:

EXAMPLE I A solution of 5.6 grams of 4-chlorophenylinocyanate, 10.0grams of Z-hydroxyethyl 1,2,2,2-tetrachloroethyl disulfide, and one dropof dibutyl tin dilaurate in S0 mls. of dry benzene were allowed to standfor one week at room temperature. The solvent was removed bydistillation, the product being heated to a maximum temperature of 100C. at 0.4 mm. Twelve grams of4-chlorophenylcarbamoyloxyethyl-l,2,2,2-tetrachloroethyl disulfide wasobtained as r an oil which slowly crystallized on standing.

Analysis. Theory: N, 3.3%. Found: N, 4.1%.

EXAMPLE II Into a flask fitted with condenser, thermometer, stirrer, anddropping funnel was introduced 8.5 grams of l,1,2,2-tetrachloroethylsulfenyl chloride in 100 ml. carbon tetrachloride. -Into the mixture cooled in an ice bath was added 3.3 grams of a 61%solution of 2-methoxyethy1 mercaptan diluted with carbon tetrachloride.The mercaptan was addded dropwise and very slowly. After addition wascompleted, the reaction mixture was refluxed for about 10 minutes. Themixture was then allowed to cool to room temperature and the solventstripped under a water vacuum. The residue was distilled yielding 4grams of methyl-B-(l,1,2,2-tetrachloroethyldithio)ethyl ether boiling ina range of 100 to 117 C. at 0.4 to 0.6 mm. mercury.

Analyzed.Theory (percent): CI, 48.8; S, 22.1. Found (percent): Cl, 46.4;S, 23.7.

The following table, Table I, lists other compounds of this inventionwhich were prepared according to general procedures known in the art.

Analysis Calculated Found structure 61? 01 s N P 01 s N P O 39 4 34.3CCl -S-SCHzCHzO ]CHa 4.4 as coi s-s-s-cm-om-o-h-nuou,

0 ..a5.s .45 ..3s.2 3.5 CHUl -CHCl-S-SCHz--CIIzOiB-NHU1 0 28.1 17 0 28.919.0 CHCl2" HClSSCH2'-' 2'- 2 5)2 0 36.2 19.1 ..358 19.9oo13-o11o1-s-s-o1r4-oH2o-ii-0o1n-o1ns---o1 0 38.8 2e 4 41.0 25.5 c01.0am s-s-oH4-01r2-0ii-s-02rr.

0 58-63 3.4 4.1 CCl CHCl-SS-CHz-CIh-O%NH--CI 0 42.5 19 3 40.3 18.6OCl;-CHC1S-SOH2OH2O%-NHCH3 0 ..a4.4 15.5 35.9 17.1 5.3CCl3CHCl-S-SCHz-CH2Oi (00211 o 5s-6u 35.9 15.2 .45 s 6.0 oo1,oHo1s-s-oHz-c1noii mr 0 -.5o.3 18.2 49.0 20.2 OOl -CllGlS-S- UHz CII O-i-OH Ol Analysis M P Calculated Found Structure o.)' 01 s N P 01 s N P-.44.6 20.1 43.3 20.5 CHClz-CClS-S-CH2OHz-O-(JCH5 ..56.2 19.7 ..35.020.0 anon-ciz-s-s-orr -orn0-c 0-oH2oH5S-Q-Cl o 39.6 21 5 .34.9 23.3 OHCl-CCl S-S-CHg-CHz-O-SCl ..3s.s 22.4 .432 26.4 CHCl -CCl SSCH CHgOCS-C H..41.3 14.0 3.3 39.2 15.6 3.1 ouch-c01T-s-s-omonzoo-Nn-o1 41.3 14.9 30.115.1 CHCh-CClz-SS-CH2CHz-O-C-NH-Q CHCl -CC1 -SSCHzCH50-CNHCHs [CHCl -CClS-S-CH2-CH2-0]2S 0 47.5 26.8 45.3 26.7

t? 7.5 5.7 CHC12-CCIz-SS-CH2CHz-oP(OC2H5)2 36.8 25.0 -.4o.7 25.4 CHC1CCl -S-S-CHz-CHzO-fi0C1H The novel compounds of this invention weretested for fungicidal activity against Pythium ultimum and Rhizoctoniasolani by means of the mycelial drop test. This test is designed tomeasure the fungitoxic activity of fungicidal chemicals in terms oftheir degree of inhibition upon mycelial growth.

Each fungitoxic compound to be tested was dissolved in acetone indilutions as indicated in the following table. Paper discs previouslyinoculated by impregnation with equal amounts of a particular fungusmycelium and placed on potato dextrose agar medium were treated byapplying a precise and equal volume of each of these fungicidalsolutions to their center. Following treatment with the fungitoxicchemical, the discs were incubated along with inoculated but untreatedcontrol discs at ambient temperatures until such time as these untreatedcontrol discs were filled with mycelial growth. Activity of thefungitoxic chemical tested was determined by comparative measurements ofradii of mycelial growth away from the edge of the disc in treated anduntreated samples. From this comparison a percentage inhibition ofgrowth area,

can be determined. The results are tabulated in columns End 11 of TableII.

The novel compounds of this invention were also compared for fungicidalactivity by means of The Standard Spore Slide-Germination Method forDetermining Fungicidal Activity. The results obtained are expressed interms of percent inhibition of germination of fungus spores.

Each compound to be treated was dissolved in acetone in dilutions to thedesired concentration. These solutions were then pipetted into the wellsof depression slides and allowed to dry. The wells were filled with aspore suspension of the test organism, Monilina fructicola, andincubated in a moist chamber overnight. A group of onehundred spores wasexamined and the number of spores germinated and not germinated wascounted and recorded to show the biological activity in terms of thepercentage germination inhibition.

The results of these tests for various chemicals of this invention onthe particular fungus mycelium and spores are indicated as shown incolumn III of Table II.

TABLE II 1 II III Pythium Rhizoctonia Monilinla Structure P.p.m. PercentP.p.m. Percent P.p.111. Percent c1 01 o 500 100 500 100 100 l l I 250100 250 100 3 100 H(J(l3SSOH OH OCCHa 125 100 150 72 1 100 01 01 o 500100 500 10 100 (11 II 2 0 80 3 62 H([) I SSCH2CHzOCOCH2CHzS Cl aH(3(|3S-SGH2CHzOOS-Cl 56 C1 C1 0 1, 000 100 1,000 100 10 100 500 100 500as 3 100 E ('3 (IJ s-s-omomo-o-s-crm-Olh 250 100 250 O1 O1 0 500 100 500100 10 100 I I II 250 100 250 33 3 100 H-o-(|:-s-s oHzoH2o-c-NH 01 12511 1 43 01 10 100 (I31 ([31 fl I 3 94 H-C|3-(|3S-SCHzCH2OONH- c1 c1 0500 100 500 10,0 10 100 I 250 100 250 100 3 100 HOCS--SCHzCHzO-CNH-OH3125 100 125 86 1 100 01 c1 0 500 100 500 94 10 100 g 250 100 250 as 3100 |J-s-s-oH2oH2o 125 100 125 22 c1 c1 0 1,000 100 1, 000 97 10 100 I AII 3 67 H- I S-SCHzCHzO 5 1 30 01 c1 0 002m 500 100 500 so 10 100 l T/250 79 250 3 100 H(|3(|3-SS-CH2CHO-P- 01 01 1. 000 100 1, 000 100 10 100H+J|JSS-CHzCHz0-S0C2Hls C1 0 1,000 100 1,000 1,000 10 100 500 100 500 78H(|](|3S-SCH2CH20CH3 250 15 Aside from the specific formulation andapplication of the class of compounds of the invention as represented bythe foregoing test, these compounds may be dispersed in or upon otherinert liquid and solid carriers such as inert clay, xylenes, etc. Thesolid carriers may be in the form of a dust, or used in conjunction witha suitable wetting agent to form a wettable powder. The fungitoxiccompounds of this invention may also be formulated with other solvents,dispersing agents, or emulsifying agents. Further, these compounds maynot only be applied alone or in mixes with other compounds of thedisclosed class, but may also be used in combination with other activetoxicants in the formulation of fungicidal compositions.

The compounds may be applied to any environmental area which is a hostto fungus or susceptible to fungus attack. For example, the fungicidalcompositions may be sprayed or otherwise applied directly to a plant orother host, may be applied to the plant seed, sprayed upon the soil orother plant environment, or used in similar ways so .as to elfect thecontrol of fungus and fungus caused diseases.

Obviously, many modifications and 'variations of the invention, ashereinabove set forth, may be made without departing from the spirit andscope thereof, and, therefore, only such limitations should be imposedas are indicated in the appended claims.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in the light of the foregoingdisclosure and discussion,

without departing from the spirit or scope of the disclosure or from thescope of the following claims.

What is claimed is:

1. Compounds having the formula where R represents a polyhaloalkyl grouphaving 1 to 2 carbon atoms and 3 to 5 halogen atoms of atomic number 17to 35, at least one of said halogens being bonded to the alpha carbonatom, X is alkylene of l to 4 carbon atoms and m is an integer varyingfrom 2 to 3.

l0 2. The compounds of claim 1 where m is 2. 3. The compounds of claim 1where R is 1,1,2,2-tetrachloroethyl.

4. The compounds of claim 1 wherein R is trichloro- 5 methyl.

5. Compound of claim 1 wherein R is 1,1,2,'2-tetrachloroethyl, m is 2and X is ethylene.

No references cited.

10 LEON ZITVER, Primary Examiner L. DE CRESCENTE, Assistant Examiner

